Ferroelectric Texture of Individual Barium Titanate Nanocrystals.

Ferroelectric materials display exotic polarization textures at the nanoscale that could be used to improve the energetic efficiency of electronic components. The vast majority of studies were conducted in two dimensions on thin films that can be further nanostructured, but very few studies address the situation of individual isolated nanocrystals (NCs) synthesized in solution, while such structures could have other fields of applications. In this work, we experimentally and theoretically studied the polarization texture of ferroelectric barium titanate (BaTiO3, BTO) NCs attached to a conductive substrate and surrounded by air. We synthesized NCs of well-defined quasicubic shape and 160 nm average size that conserve the tetragonal structure of BTO at room temperature. We then investigated the inverse piezoelectric properties of such pristine individual NCs by vector piezoresponse force microscopy (PFM), taking particular care to suppress electrostatic artifacts. In all of the NCs studied, we could not detect any vertical PFM signal, and the maps of the lateral response all displayed larger displacement amplitude on the edges with deformations converging toward the center. Using field phase simulations dedicated to ferroelectric nanostructures, we were able to predict the equilibrium polarization texture. These simulations revealed that the NC core is composed of 180° up and down domains defining the polar axis that rotate by 90° in the two facets orthogonal to this axis, eventually lying within these planes forming a layer of about 10 nm thickness mainly composed of 180° domains along an edge. From this polarization distribution, we predicted the lateral PFM response, which was revealed to be in very good qualitative agreement with the experimental observations. This work positions PFM as a relevant tool to evaluate the potential of complex ferroelectric nanostructures to be used as sensors.

Morphogenesis mechanisms in the solvothermal synthesis of BaTiO3 from titanate nanorods and nanotubes.

A rich variety of single crystalline BaTiO3 (BT) nanostructures have been synthesized by two different routes using titanate nanorods and nanotubes as precursors. Free standing, mixed or agglomerated nanotori, solid or hollow nanospheres and nanocubes were obtained. A careful analysis of the shape evolution of the resulting BT nano-objects obtained with both types of precursors and different parameters (precursor composition and shape, temperature, Ba/Ti molar ratio) allowed an improved understanding of the nanostructure formation. The morphogenesis models at play such as Ostwald ripening and the Kirkendall effect have been identified. Other mechanisms hereafter called the self and merging rebuilding processes and a tentative Turing-reaction-diffusion-model are proposed to explain the formation of these obtained nanoparticles.